Procedure for the production of yellow dye images by color development



May 15, 1962 L. BURGARDT ETAL PROCEDURE FOR THE PRODUCTION OF YELLOW DYE IMAGES BY COLOR DEVELOPMENT Filed July 31, 1958 FIGJ a 2 Lu 0 600 700 WAVELENGTH (MILLIMICRONS) t m FIG-2 Z Lu 0 I 6G0 700 WAVELENGTH (MILLIMICRONS) 2 a 2 Lu 0 l wAvELENGTH (MILLIMICRONS) 8 FlG.4

INVENTORS LoTHAR BURGARDT o WILLIBALD PELZ 400 500 600 OTTMAR wAHL WAVELENGTH MILLIMICRONS 7 k BY United States Patent 3,034,891 PROCEDURE FOR THE PRODUCTION OF YEL- LOW DYE IMAGES BY COLOR DEVELOPMENT Lothar Burgardt, Munich, and Willibald Pelz and Ottmar Wahl, Opladen, Germany, assignors to General Aniline & Film Corporation, New York, N.Y., a corporation of Delaware Filed July 31, 1958, Ser. No. 752,331 9 Claims. (Cl. 96-55) This invention relates to color photography and, more particularly, to the development of yellow dyestuif images.

It is already known to use color formers for the production of dye images. These color formers are added to the photographic emulsion or to the developer and yield in the course of the development of the latent silver image azomethine or quinoneimine dyes through coupling with the oxidation products of the color develop ing agent. This principle of color forming development is of great technical importance for the production of photographic multicolor pictures in multilayer materials. The image color of the three part images should be adjusted in such a way so as to correspond to the theoretical requirement of the subtractive three color photography. For instance, it is desirable that the color couplers or components used for the formation of the yellow image combine with the oxidation products of the color developer in such a way that dyes are formed which absorb only blue light, but transmit red and green light as completely as possible. The conventional color developers of the p-phenylenediamine type which were used mostly in combination with acetoacetanilides and benzoylacetanilides met these requirements to a large extent.

It has recently been proposed to use as color formers compounds which correspond to the following general formula:

and

o-NH,

wherein Z represents the atoms necessary for the completion of a heterocyclic ring structure. Among these developers are 4-amino-5-pyrazolenes which are further substituted by a variety of substituents in the land 3- position. Of special importance are those compounds which carry in the 3-position a carboxy or substituted carboxy group such as, for example, an esterified carboxy group; a carboxamido group which can be further substituted on the nitrogen atom; a carbohydrazido or an N- substituted carbohydrazido group. These developing agents are characterized by the following general formula:

wherein R represents a carboxy group or a substituted carboxy group including carbox-amino, carbalkoxy and carbohydrazino groups, and R represents hydrogen, or an alkyl, aryl or heterocyclic group. These developers couple with 3-alkyl-5-pyrazolones as illustrated, for instance, by l-(p-phenoxy-m'-sulfophenyl)-3-stearyl-5-pyrazolone to form magenta dyes of brilliant color which excel also by their exceptionally high transmission for blue and red. The shade of these dyes resembles essenice tially that of the dyes which are obtained by color development of the aforesaid pyrazolone couplers with p-phenylenediamine' color developers, but the absence of the secondary absorption maximum in the shorter wave range eliminates or at least drastically reduces the undesired secondary absorption in the blue region of the spectrum.

However, up to now it was impossible to produce with the 4-amino-5-pyrazolone developers any yellow dyes which could be used satisfactorily in multilayer materials. The acetoacetanilides and benzoylacetanilides derivatives, which had previously been used with p-phenylenediamine developers, yielded with the aforesaid 4-amino-5- pyrazolone color developer only dyes which were entirely unsatisfactory because their range of absorption Was shifted entirely too far into the long wave region. In addition to this disadvantageous shift of the absorption maximum which amounted to as much as millimicrons, it was further found that these dyes were characterized by an excessively high content of gray.

We have found that excellent yellow color images are obtained in silver halide emulsion layers by using as color developer a compound having the following general formula:

wherein Z represents the atoms necessary to complete a heterocyclic ring system, particularly a 4-amino-5-pyrazolone system as defined above, in the presence of a cyanoacetamino type color former which is unsubstituted in the two ortho positions relative to the amino group, but carries a substituent in the metaor parapositions. These color formers are characterized bv the following general formulae:

and

CN-CHi-CO-NlEP-Oi :Y

wherein X represents the atoms necessary to complete an aromatic nucleus of the benzene or naphthalene series which carries at least one of the positions other than the ortho position, namely in the metaor parapositions a suitable substituent such as an alkyl group, e.g., methyl, ethyl, propyl, iso-propyl, butyl and the like; an alkoxy group, e.g., methoxy, ethoxy, propoxy, octadecoxy and the like; an aryl group, e.g., phenyl, naphthyl and the like; a heterocyclic group, e.g., benzothiazolyl, benzoxazolyl; and a substituted amino group such as an alkylor arylamino group, e.g., dimethylamino, methyl-hexadecyl-amino, methyloctadecylamino, phenylamino and the like; an acylamino group, e.g., acetylamino, propionylamino, benzoylamino and the like; an N-substituted sulfonamido group, e.g., N-phenylsul-fonamido, N-thiazolylsulfonamido and the like; an N-substituted carboxamido group, e.g., N-phenylcarboxamido, N-methylcarboxamido and the like; Y represents the atoms necessary to complete a heretocyclic ring system such as a thiazole, benzothiazole, benzoxazole, beuzimidazole, pyridine, quinoline, triazole or benzotriazole system. These aromatic and heterocyclic nuclei can be further substituted by water solubilizing groups such as sulfonic and carboxylic groups or by additional groups which render them fast to diffusion such as aliphatic chains with at least 10 carbon atoms, e.g., decyl, dodecyl, tetradecyl, hexadecyl, octadecyl and the like.

as components for color development. However, they did not find any practical use because they did not give any acceptable dyes when developed with the conventional diamines or aminophenoles. The dyes obtained are generally orange-red or red, have a very high content of gray, a flat gradation and poor speed characteristics.

The compound 3-cyanoacetamino-4-Nmethyl-N-octadecylaminobenzoic acid is already known. However, when this compound is coupled with 4-amino-5-pyrazolone developers, the dyes obtained cannot be used satisfactorily in photographic multilayer materials because these dyes are on the reddish side, absorb appreciable amounts of green light and thus prevent any correct reproductions.

It came as a total surprise when it was found that the cyanoacetamides which were known to be completely useless when developed with conventional phenylenediamines yielded yellow dyes of excellent brilliance when developed with the heterocyclic 4-amino-5-pyrazolones. As a matter of fact, earlier work with benzoyl acetanilides would have lead to expect a pronounced shift toward the longer wave length region. The new yellow dyes have the further advantages that they are very stable under conditions of heat and high humidity as they prevail in the tropics. They are less subject to bleaching by direct sunlight than the azomethines which are formed by the interaction of benzoylacetanilides or acetoacetanilides and phenylenediamines.

We were able to establish that cyanoacetanilides carry in oltho position to the cyanoacetamino group a suitable substituent such as an alkoxy, alkylamino or acylamino group, yield yellow dyes which transmit far less green light than dyes obtained from cyanoacetanilides which are substituted in the metaor parapositions. The shift of the maximum of the dyes prepared from the orthoand parasubstituted cyanoacetanilide is very pronounced and amounts to at least 30 millimicrons. The extent of this shift depends, to a certain extent, on the developer used, but is also very much pronounced.

Among the suitable developing agents, the following are suggested:

4-amino-3-carboxamldo-1- (2methylpheny1)-5-pyrazolone HeNO CC OH-NI-I2 II N 4-amino-3- N-B-hydroxyethyl) carboxamld o-1-pheny1-5- .pyrazolone The cyanoacetanilides can be added to the color developer solution so that the dyes formed during color development are formed in insoluble forms in the exposed areas of the gelatin layer. Those couplers, which are added to the emulsion, are provided in the known manner with substituents which prevent the diffusion or migrations of the color former from its own layer to a neighboring layer. Suitable for this purpose are aliphatic chains with at least 12 carbon atoms, or such other substituents which are known to render color formers fast to diffusion. In order to facilitate the incorporation of the color formers in the emulsion, it is advantageous to provide them with groups which render than soluble in alkali, such as carboxylic or sulfonic acid groups.

The following is a suggestive listing of cyanoacetamino color formers which may be employed for the formation of yellow azomethine dye images:

C O 0 H 3-cyanoacetamidobenzene-su1fonamid0benzene-2car-bonito acid II IfiI (3H ONCHzCONH-SnNHNC on S 4-cyan0acetamidobenzene-sulfonamido-Z'-thiazo1e III N CN-CH9C O-NH- (J-CH3 5-eyanoacetamido-2-methy1benzothlazole IV CN CHT-CONH NH-C OCHzCN 1,5-dtcyanoacetiaimidonaphthaline V /C1a a1 CNCHaCO-NH N\ CH; S 0 H 4- N-methyl-Noctadecylamino) -cyanoacetamidobenzene- 3-sulf0nic acid v1 0 N-CNz-C ONH-QS o 2-NHQOC1BHU s 0 3H 4- (4.-cyanoacetamidobenzeneosulfonamido) -octadecoxybenzene-2-sulfouic acid VII /C 5H 0 N-O m-o 0 -N HO 0 o -NnC -N l CH3 SO H 4- (4'-cyanoacetamidobenzoylamido) -N-methyl-N-octadecylaniline-Z-sulfonic acid SO 3H '4- 3 -cyanoacetamidobenzoylamido) -N-methy1-N-octadecylaniline-Zeulfoni c acid 4- (4-cyanoacetamidobenzene-sulfonamido) -N-methy1-Noctadecyl'aniline-2-sulfonic acid 2- 3'-cyan0acetamidopheny1) -3-octadecylbenzimidazole-G- sulfonic acid 4- (N -carboxymethyl-N-octadecyl) -cyanoacetamidobenzene-3- sulfonic acid S H 4-stearylamidm2-su1fonic4-cyanoaceta mido-diphenylamine -m-Cyanoacetamidoanisole ON-CHa-C O-NH 3 CNCHz-C O-NH 1,3*dicyan0acetamidobenzene XVIII XIX 0 12 31 4- (N-methyl-N-octadecyl) -cyanoacetamidobenzene-3- carboxylic acid The compounds can be prepared according to several known procedures. Convenient and generally useable is the reaction of esters of cyanoacetic acid with aromatic or heterocyclic amines. This reaction can be carried out in the absence of a solvent at temperatures ranging from C. to 200 C. as described in Beilstein, vol. XII, page 294, or by using a suitable solvent under reflux conditions. Amines which carry alkali-solubilizing substituents such as sulfonic or carboxylic acid groups are reacted in pyridine or other weakly alkaline solvents or basic condensing agents, while distilling off the alcohol which is formed during the reaction.

Other suitable methods include the reaction of the desired amine with cyanoacetyl chloride or cyanoacetic acid in the presence of phosphorous oxychloride (Journ. f. prakt. Chem, vol. 25, page 232) or the reaction of the amino group with chloroacetyl chloride and the conversion of the chloromethylene group into the cyanomethylene group.

The invention is further illustrated by the following examples:

Example I A silver halide emulsion coated on a cellulose ester support was exposed through a step wedge and developed 1-phenyl-4-amino-5-pyrazolone-3-carboxamide sulfate (color developer) Water to make 1 liter.

The developed film was bleached, fixed, washed and dried. A yellow dye image with an absorption maximum at 460 millimicrons was obtained.

The 3-cyanoacetamidobenzene-sulfonamidobenzene-Z- carboxylic acid was prepared as follows:

58 grams of 3-aminobenzene-sulfanilide-2-carboxylic acid was dissolved in 250 milliliters of dry pyridine and treated with 30 grams of ethyl cyanoacetate. The mixture was heated for 10 hours under reflux while distilling off slowly 150 milliliters of a pyridine-ethanol mixture. The residue was acidified with hydrochloric acid, ice was added and the mixture stirred until the oil which separated had crystallized. The product was filtered, dried and recrystallized from glacial acetic acid. Melting point 194-197" C.

Example [1 Example I was repeated while using in place of the color former, 1 gram of 4cyanoacetamidobenzene-sulfonamido-2'-thiazole, and using in place of the color developer, 6 grams of 1-(2-chlorophenyl)-3-carbethoxy-4- amino-S-pyrazolone hydrochloride. A strongly colored yellow dye image with an absorption maximum at 455 millirnicrons was obtained.

The 4-cyanoacetaminobenzene-sulfonamino-2'-thiazole was prepared as follows:

A mixture of 76.6 grams of 4-aminobenzenesulfonamino-2'-thiazole (M.P. ZOO-202 C.), 41 grams of ethyl cyanoacetate and milliliters of pyridine were stirred for 4 /2 hours under reflux. Subsequently, 50 milliliters of a pyridine-alcohol mixture were distilled ofl during a period of about two hours. When ice and dilute hydrochloric acid were added to the residue, 2. resinous product precipitated. It was re-dissolved in a hot 1 percent solution of sodium hydroxide, diluted with water to 1 liter, purified with charcoal and precipitated in the cold with dilute hydrochloric acid. The precipitate was filtered, dried and recrystallized from a small amount of glacial acetic acid. Melting point 146 (dec.).

7 Example III Example II was repeated with the exception that the color former was replaced by 1 gram of S-cyanoacetamido-2-methylbenzothiazole. A yellow dye image with an absorption maximum at 458 millimicrons was obtained.

The S-cyanoacetamido-2-methylbenzothiazole was prepared as follows:

A mixture of 49 grams of 5-amino-2-methylbenzothiazole, 41 grams of ethyl cyanoacetate and 150 milliliters of xylene were heated under moderate reflux for 5 hours. Eighty milliliters of the alcohol-xylene mixture was gradually distilled off over a period of 2 to 3 hours. The residue was allowed to cool; the crystals which formed were filtered, washed with ether and recrystallized from 400 milliliters of ethanol with charcoal (M.P. 226- 70 Example IV Example I was repeated while using as the color former, 1 gram of 1,S-dicyanoacetamidonaphthaline and using as the color developing agent, 6 grams of 1-phenyl-4-amino- 3-carbethoxy-5-pyrazolone sulfate. A yellow dye image was obtained which had an absorption maximum at 452 millimicrons. In this instance, the color former was first dissolved in a small amount of methanol and diluted sodium hydroxide and then added to the developer solution.

The 1,5-dicyanoacetamidonaphthaline was prepared as follows:

A mixture of 30 grams of 1,5-naphthalenediamine and 55 grams of ethyl cyanoacetate was heated for 2 hours under reflux. The mixture was then cooled to about 60 C., and methanol was added with stirring. The crystals which formed were washed with a small amount of methanol and dried; M.P. 173 C.

Example V Grams Potassium carbonate 75 Sodium sulfite (anhydrous) 10 Potassium 1 3-carbethoxy-4-amino-5-pyfia2olone-dihydr0chloride I Water to make 1 liter.

The developed picture was bleached, fixed, washed and dried. A yellow dye image, having an absorption maximum at 445 millimicrons, was obtained. The above yellow coupler was prepared as follows: A mixture of 800 milliliters of water, 220 grams of sodium salt of 4-nitrochlorobenzene-Z-sulfonic acid, 68 grams of sodium bicarbonate, 228 grams of methylstearylamine and 200 milliliters of methanol was heated for 12 hours under reflux with stirring. The hot solution was poured into 1000 milliliters of methanol and stirred until cold. The precipitate was filtered off and washed with methanol. Yield: 400 grams.

Fifty grams of the sodium salt of 4-nitro-N-methy1 N-octadecylaniline-2-sulfonic acid was diluted with 400 milliliters of methanol; Raney nickel was added as a catalyst and the mixture hydrogenated at 6070 C. in a stirrer-equipped autoclave. The hot hydrogenated solution was filtered off and acidified with glacial acetic acid. The amine which precipitated in crystalline form was washed with glacial acetic acid and recrystallized from methanol. Yield: 30 grams. Melting point: 158l66 C.

Twenty grams of the resultant 4-(N-methyl-N-octadecylamino)aniline-3-sulf0nic acid and 10.5 grams phenyl cyanoacetate were heated under vacuum to about 180 C. while distilling off the liberated phenol. The reaction was completed after about 30 minutes. The hot fusion 8 mixture was diluted with alcohol, and the precipitate filtered off. The coupler was purified by boiling it out twice with methanol. Yield: 15.2 grams.

The phenyl cyanoacetate was prepared from cyanoacetic acid, phenol and phosphorous oxychloride in analogy to the procedure described for monophenyl oxalate in the Journ. prakt. Chem, vol. 25, page 282.

Example VI A gelatinous silver halide emulsion containing 15 grams of 4-(4'-cyanoacetamidobenzene-sulfarnido)-octadecoxybenzene-Z-sulfonic acid per liter of liquid emulsion was coated, dried, exposed and then developed in a developer which was identical with that of Example V, except that its color developing agent had been replaced by 6 grams of 1-(m'-chlorophenyl)-4-amino-3- carbethoxy-S-pyrazolone. After bleaching, fixing, washing and drying, a brilliant dye image was obtained which had an absorption maximum at 450 millimicrons.

The above color former was prepared as follows:

22.5 grams of 4-octadecoxyaniline-3su.lfonic acid was mixed with a small amount of methanol and dissolved in an adequate amount of 10 percent sodium hydroxide solution. A concentrated solution of 14.5 grams of pnitrobenzenesulfonyl chloride in acetone was added dropwise with stirring. The solution was kept alkaline to phenolphthalein by the gradual addition of a 10 percent sodium hydroxide solution. The temperature was maintained at l5-20 C. After one hour, the solution was added to a mixture ice and hydrochloric acid, filtered with suction and washed with water. 50 grams of the nitro-compound thus obtained was added to 400 milliliters of methanol while adjusting the pH to a value between 7.5 and 8.0 with a 10 percent sodium hydroxide. It was hydrogenated in a stirrer-equipped autoclave at 60-70 C. using Raney nickel as the catalyst. The solution was filtered and acidified with glacial acetic acid. The amine which precipitated was filtered off, Washed with glacial acetic acid and recrystallized from methanol. Yield: 25 grams; M.P. over 270 C.

A mixture of 12 grams 4-(4'-aminobenzenesulfonamino)-octadecoxybenzene-2-sulfonic acid, 2.2 grams of methyl cyanoacetate and 100 milliliters of anhydrous pyridine were stirred for 5 hours at 90 C. Forty milliliters of a pyridine-methanol mixture was distilled off. One milliliter of methyl cyanoacetate and 40 milliliters of pyridine were added and 30 milliliters of solvent distilled off; finally 1.5 milliliters of methyl cyanoacetate and 35 milliliters of pyridine added and finally 45 milliliters were slowly distilled off. The residue was diluted with 300 milliliters of ice water and 150 milliliters of methanol and added with stirring to dilute hydrochloric acid. The precipitate was filtered off, dissolved in glacial acetic acid, treated with charcoal, diluted with water, precipitated with a sodium chloride solution; heated briefly to C., cooled, filtered and washed with water. The yield was 7.0 grams.

The 4-octadecoxyaniline-3-sulfonic acid can be prepared in the following manner:

A solution of 165 grams of p-acetylaminophenol and 340 grams of octadecylbromide in 2000 milliliters of absolute ethanol is treated with a solution of 24 grams of sodium in 500 milliliters of absolute ethanol. The resultant solution is heated for 12 hours under reflux, treated hot with methanol, cooled, filtered and washed with methanol. M.P. 9397 C.

Seventy-five grams of this product was dissolved in 38 milliliters of ethanol, treated with grams of a 50 percent potassium hydroxide solution and boiled for 8 hours until deacetylated. The solution was poured into a mixture of ice and 1.4 liters of 20 percent sulfuric acid. The precipitate which formed was filtered off, washed with water and recrystallized from glacial acetic acid. M.P. l97207 C.

Forty-three grams of the amine sulfate was sulfonated by treatment with a mixture of 150 milliliters of concentrated sulfuric acid and 150 milliliters of 20 percent fuming sulfuric acid for 1 hour at 25 C. The sulfonation mixture was treated with ice, the sulfonic acid filtered 01f, boiled out first with alcohol and then with glacial acetic acid, filtered and washed.

Example VII A liquid gelatin silver halide emulsion which contained 15 grams of 4-(4'-cyanoacetam-idobenzoylacetamido)-N-methyl-N-octadecylanilineZ-sulfonic acid per liter was coated, dried, exposed and developed in the developer described in Example V, which contained as the developing agent 0.6 gram of 1-(o-chlorophenyl)- 4-arnino-3-canbethoxy-5-pyrazolone.

The developed picture was bleached, fixed, washed and dried. A very pure yellow image, having an absorption maximum at 445 millimicrons, was obtained.

The coupler was prepared as follows:

A solution of 21 grams of 4-(N-methyl-N-octadecylamino)-aniline-3-sulfonic acid, 200 milliliters of pyridine (anhydrous) and 14.5 grams of p-nitrobenzoyl chloride in dry acetone was acylated in the usual manner at room temperature. The solution was diluted with 200 milliliters of methanol and stirred into a mixture of ice and 10 percent hydrochloric acid. The resultant precipitate was filtered ofi, boiled out with methanol, cooled and filtered olf.

A solution of 33 grams of the nitro compound was added to 400 milliliters of methanol and the pH adjusted to 8.0 with 5 milliliters of concentrated sodium hydroxide solution.

Hydrogenation was carried out in the usual manner with hydrogen, using Raney nickel as a catalyst. The filtrate was treated with glacial acetic acid to precipitate the amine. Yield: 27.0 grams. The amine was reacted with methyl cyanoacetate as described in Example VI and recrystallized from ethanol. M.P. 133139 C.

Example VIII Example VII was repeated except that 4-(3'-cyanoacetamidobenzoylamido)-N-methyl N octadecylaniline- 2-sulfonic acid was used as a coupler. A lemon-yellow dye with an absorption maximum at 425 millimicrons was obtained.

The coupler was prepared in analogy to the procedure described in Example VII except that m-nitrobenzoyl chloride was used.

The reaction of the amine with cyanoacetic acid can be carried out conveniently in the following manner:

11.4 grams of 4-(m'-aminobenzoylamino)-N-methyl- N-octadecylaniline-Z-sulfonic acid, 2.2 grams of cyanoacetic acid and 150 grams of phosphorous oxychloride were mixed with stirring until the temperature reached 60 C. Stirring was continued for 1 hour at 70-80 C. Water was carefully added and the precipitate filtered off and washed with water. The coupler was triturated with hot methanol, filtered and dried.

Example IX A silver halide emulsion containing 15 grams of benzenesulfonamido N-methyl-N-octadecylaniline-Z-sulfonic acid per liter was coated on a film base, dried, exposed and developed in a developer as described in Example V which contained as the color developing agent 1-(o'-tolyl)- 4-amino-3-carboxamido-5-pyrazolonehydrochloride. The developed material was bleached, fixed, washed and dried. A brilliant yellow dye image was obtained. It had an absorption maximum at 450 millimicrons with very steep slopes.

This coupler was prepared as follows:

Twenty-one grams of 4-(N-methyl-N-octadecylamino)- aniline-3-sulfonic acid was reacted with 15 grams of p-nitrobenzenesulfochloride as described in Example VI. The nitro compound was purified by recrystallization from ethanol. The conversion of the nitro group into the amino group can be carried out by catalytic hydrogena= tion with Raney nickel as described, for instance, in Example VI. The reaction of the amine with methyl cyanoacetate in the presence of pyridine is also carried out according to the procedure described in Example VI. The coupler which was recrystallized from ethanol softens at C. and melts at 203 C.

Example X A silver halide emulsion layer containing the color former 2-(3'-cyanoacetamidophenyl) 3 octadecylbenzimidazole-6-sulfonic acid was exposed and processed with a developer containing 5 grams of 1-phenyl-4-amino-3- N-(fi-hydroxyethyl)-carboxamido-S-pyrazolone. The developed mixture was bleached, fixed, washed and dried. A yellow image with a slight reddish hue was obtained which had an absorption maximum at 465 millimicrons.

The coupler was prepared as follows:

2-(3'-aminophenyl) 3 octadecylbenzimidazole-6-sul fonic acid was reacted with methyl cyanoacetate in pyridine as described in Example VI. The precipitated coupler was purified by boiling it with methanol. The amine is prepared in accordance with the procedure described in United States Patent 2,500,467. It can be easily purified by recrystallizing it from methanol.

Example XI Example X was repeated, except that prior to color development, the layer was first developed in a black and white, metol hydroquinone developer, then short-stopped, rinsed and reexposed. A positive yellow image was obtained.

The invention is further illustrated by the following drawing showing the spectral characteristics of our new dyes. More particularly, FIG. I shows a comparison of the absorption curves of the dyes formed from 4'-stearylaminobenzoylacetanilide-3,S-dicarboxylic acid (curve 11) and 4'-(cyanoacetamidobenzenesulfonamido)octadecoxybenzene-Z-sulfonic acid (curve 12) when developed with 1- (2-chlorophenyl -4-amino-3-carbethoxy-S-pyrazolone.

FIG. II shows a comparison of the absorption curves of the dyes formed by the development of Z-(N-methyl- N-octadecylamino) -4'-anisoylacetanilido-5-carbonic acid (curve 13) and 4-(N-methyl-N-octadecylamino)-cyanoacetamidobenzene-3-sulfonic acid (curve 14) by development with 1-phenyl-4-amino 3 carboxamido-S-pyrazolone.

FIG. III shows a comparison between the two dyes formed by the development of 4 N-methyl-N-octadecylamino-3-sulfo-cyanoacetanilide (curve 15) and 2-N-methyl-N-octadecylamino-S-sulfo-cyanoacetanilide (curve 16) when developed with 1-phenyl-4-amino-3-carboxamido-5- pyrazolone.

FIG. IV shows the spectral characteristics of the dyes formed by development of 4-(N-methyl-N-octadecylamh no)-cyanoacetaminobenzene-3-sulfonic acid with p-dimethylaminoaniline (curve 17) and 1-(o'-tolyl)-4-amino- 5-pyrazolone-3-carboxamide (curve 18).

Various modifications of this invention will occur to persons skilled in the art. We, therefore, do not intend to be limited in the patent granted except as necessitated by the appended claims.

We claim:

1. The method of producing yellow dyestufi images in a silver halide emulsion layer which comprises exposing the layer and developing it with a 4-amino-5-pyrazolone developing agent in the presence of a dye coupler having a cyanoacetamido group and selected from the class consisting of those characterized by the following formulae:

wherein X represents the atoms necessary to complete an aromatic nucleus of the benzene and naphthalene series which carries a substituent in a position other than the orthoposition relative to said cyanoacetamido group, said substituent being selected from the class consisting of alkyl, alkoxy, benzothiazolyl, benzimidazolyl, alkylamino, diethylamino, arylamino, carboxy, sulfo, acylamino, sulfonamido and carboxamido groups, and wherein Y represents the atoms necessary to complete a heterocyclic nucleus containing at most two nuclei, and being selected from the class consisting of thiazole, benzothiazole, benzoxazole, benzimidazole, pyridine, quinoline, triazole and benzotriazole radicals.

2. The method according to claim 1, wherein said developing agent is l.-phenyl-4-amino-3-carboxamido-5- pyrazolone and wherein said color former is 3-cyanoacetamidobenzene-sulfonamidobenzene-Z'-carboxylic acid.

3. The method of producing a yellow dye image in a silver halide emulsion layer which includes exposing the layer and developing it with a developer solution containing 3-carbethoxy-4-amino-5-pyrazolone in the presence of 4-(N-methyl-N-octadecylamino)-cyanoacetamidobenzene-S-sulfonic acid.

4. A color forming photographic developer comprising a 4-amino-5-pyrazolone developing agent and a color former having a cyanoacetamido group selected from the class consisting of those having the following general formulae:

oN-oIn-c ONH-C :X

and

wherein X represents the atoms necessary to complete an aromatic nucleus of the benzene and naphthalene series which carries a substituent in a position other than the orthoposition relative to said cyanoacetamido group, said substituent being selected from the class consisting of alkyl, alkoxy, benzothiazolyl, benzimidazolyl, alkylamino, dialtylamino, arylamino, carboxy, sulfo, acylamino, sulfonamido and carboxamido groups and wherein Y represents the atoms necessary to complete a heterocyclic nucleus containing at most two nuclei, and being selected from the class consisting of thiazole, benzothiazole, benzoxazole, benzirnidazole, pyridine, quinoline, triazole and benzotriazole radicals.

5. A color forming developer solution containing as the developing agent l-phenyl-4-amino-3-carboxamido-5- pyrazolone and containing as a color former for the yellow image the compound 3-cyanoacetamidobenzenesulfonamidobenzene2-carboxylic acid.

6. The method of producing yellow dyestulf images in a silver halide emulsion layer containing a color former fast to diffusion having a single cyanoacetamido group and selected from the class consisting of those corresponding to the following general formulae:

wherein X represents the atoms necessary to complete an aromatic nucleus of the benzene and naphthalene series which carries a substituent in a position other than the orthoposition relative to said cyanoacetamido group,

said substituent being selected from the class consisting of alkyl, alkoxy, benzothiazoyl, benzimidazolyl, alkylamino, dialkylamino, arylamino, carboxy, sulfo, acylamino, sulfonamido and carboxamido groups, and wherein Y represents the atoms necessary to complete a heterocyclic nucleus containing at most two nuclei, and being selected from the class consisting of thiazole, benzothiazole, benzoxazole, benzimidazole, pyridine, quinoline, triazole and benzotriazole radicals which comprises exposing said layer, and developing it with a color developer containing as a developing agent a 4-amino-5- pyrazolone.

7. The method of producing a yellow dyestuif image in a silver halide emulsion containing as a color former fast to diffusion the compound 4-(N-methyl-N-octadecylamino)-cyanoacetamidobenzene-B-sulfonic acid, which comprises developing it in a developer solution containing 4-amino-3-carbethoxy-5-pyrazolone as the developing agent, bleaching, fixing and washing said layer.

8. The method of producing yellow dyestulf images in a silver halide emulsion layer containing a color former fast to diffusion having a single cyanoacetamido group and selected from the class consisting of those corresponding to the following general formulae:

wherein X represents the atoms necessary to complete an aromatic nucleus of the benzene and naphthalene series which carries a substituent in a position other than the orthoposition relative to said cyanoacetamido group, said substituent being selected from the group consisting of alkyl, alkoxy, benzothiazolyl, benzimidazolyl, alkylamino, dialkylarnino, arylamino, carboxy, sulfo, acylamino, sulfonamido and carboxamido group and wherein Y represents the atoms necessary to complete a heterocyclic nucleus containing at most two nuclei, and being selected from the class consisting of thiazole, benzothiazole, benzoxazole, benzimidazole, pyridine, quinoline, triazole and benzotriazole radicals, which comprises exposing said layer to an original, developing the exposed layer in a black and white developer incapable of coupling with said coupler compound, exposing the undeveloped silver halide and developing it with a color developer containing as the developing agent a 4-amino-5-pyrazolone which is sub stituted in the 3-position by a member selected from the group consisting of carbalkoxy, carboxy and carboxamido groups.

9. The method of producing a yellow dyestuif image in a silver halide emulsion containing as a color former fast to diffusion the compound 4-(N-methyl-Noctadecylamino) cyanoacetamidobenzene 3-sulfonic acid, which comprises developing it in a black and white developer incapable of coupling with said color former, exposing said layer through a pattern, developing it in a developer solution containing 4-amino-3-carbethoxy-5-pyrazolone as the developing agent, bleaching, fixing and washing said layer.

References Cited in the file of this patent UNITED STATES PATENTS 2,182,815 Middleton et al Dec. 12, 1939 FOREIGN PATENTS 1,124,976 France Oct. 22, 1956 

1. THE METHOD OF PRODUCING YELLOW DYESTUFF IMAGES IN A SILVER HALIDE EMULSION LAYER WHICH COMPRISES EXPOSING THE LAYER AND DEVELOPING IT WITH A 4-AMINO-5-PYRAZOLONE DEVELOPING AGENT IN THE PRESENCE OF A DYE COUPLER HAVING A CYANOACETAMIDO GROUP AND SELECTED FROM THE CLASS CONSISTING OF THOSE CHARACTERIZED BY THE FOLLOWING FORMULAE: 